Single pad thermal process for dyeing textile fibers



United States Patent Ofi ice 3,184,282 Patented May 18, 1965 This invention relates to compositions of matter useful as reactive dyes for materials possessing in their structure exchangeable hydrogen atoms. More particularly, this invention deals with dyes for textile fibers and similar organic materials (including paper, leather, plastic film, etc.) which possess in their molecules or micelles reactive radicals such as OH, NH or NH Common illustrations of such materials are cellulosic fiber, wool, silk, nylon fiber and polyvinyl alcohol film.

It is an object of this invention to provide novel chemical compounds adapted for use as fiber-reactive dyes. Another object is to provide fiber-reactive dyes which are versatile in the sense that they can be applied to the fiber by various standard methods such as padding, exhaust and printing procedures. A further object is to provide fiberreactive dyes which can be manufactured economically and which generally give rapid and high fixation on cellulosic fibers. Still another object is to provide fiberreactive dyes which possess good build-up qualities and which produce dyeings that are fast to light and to washing. Other objects and achievements of this invention will appear as the description proceeds.

By rapid fixation in this application, we mean essentially complete fixation after 0.5 to one minute. (This quality is of interest primarily in padding procedures.) By high fixation, we mean that about 70 to 100% of the dye is chemically ponded to the fiber.

Reactive dyes constitute a type of dyes of relatively recent development. In these dyes, the dyeing capacity depends, not on physical aflinity between the dye and fiber, but on direct chemical reaction (with formation of covalent bonds) between the dye and certain reactive radicals in the fiber. Such dyes generally have the form Sol.

wherein D is the essential radical of a dye molecule, in other words, a radical containing a chromophoric group; S01. is a solubilizing group, such as sulfo or carboxy; and Q is a reactive radical through which the dye molecule is reacted with the OH groups or NH or NH groups of the fiber.

Heretofore, monochloroand dichlorotriazine radicals have generally been used as reactive radicals, although others have been suggested or actually used.

Now, according to the present invention, new chemical compounds are produced which may be used as reactive dyes on fiber or other organic material as aforementioned, and satisfying to a high degree the aforenoted objects and improvements. The new chemical compounds may be expressed by the general formula where D is the radical of a Water-soluble dye chromophore, particularly of an azo, metallized azo, acid-anthraquinone, or phthalocyanine coloring matter; R is hydrogen, a lower alkyl radical (say, 1 to 4 C-atoms) or a Z-hydroxyethyl, Z-cyanoethyl or 2-sulfotoethyl radical (free acid or water-soluble salt); and Q is the radical of a beuzodiazine of the group consisting of quinoxalines and phthalazines bearing two halogen atoms in the heterocyclic ring and being attached to the CO group in the above formula in the benzo ring.

More partciularly, Q is a dihalogenobenzodiazine radical of the group defined by the formulas wherein each X individually designates C1 or Br.

The novel dye compounds of this invention are readily and economically prepared by reacting a water-soluble amino-dye compound of the formula D-NHR, wherein D and R have the same meaning as above, with a B2- carbonyl halide of a benzodiazine compound as above defined, in other words, a compound of the formula QCO-hal., wherein hal. represents a halogen atom such C1 or Br while Q is a benzodiazine compound selected from the group above set forth. The reaction is achieved by bringing the two reactants together in aqueous solution at room temperature (or higher, if desired, up to say C.), in the presence of an alkali-metal carbonate or other convenient acid-binding agent (NaOH, Na PO pyridine, etc.) in sufficient quantity to drive the condensation forward at a reasonable rate. Customarily, a pH between 6 and 10 will answer this purpose. The reaction product is recovered by salting out and filtering, in the usual manner.

The requisite dihalogeno benzodiazine carbonyl halide itself may be prepared by the action of a phosphorus pentahalide or oxyhalide on the corresponding dihydroxybenzodiazine carboxylic acid. Dihalogeno benzodiazine carbonyl halides wherein the two X-atoms are unlike may be obtained in the same manner except using a mixture of phosphorus pentachloride and phosphorus pentabromide, for instance, or of phosphorus oxychloride and phosphorus oxybromide.

In the cases where D is an azo dye, other methods of synthesis are also available; for instance, (1) condensing the benzodiazine carbonyl halide with an azo-dye coupling component, and then coupling the condensed product to a diazotized arylamine or azoarylamine compound, (2) condensing the benzodiazine carbonyl halide, in equimolecular proportions, with an aryl diamine; diazotizing the resulting monoamine, and coupling to a coupling component; or (3) development of the dye on the fiber, after the latter has been reacted with a coupling or diazo component which carries a dihalogeno benzodiazine carbonyl radical.

The application of our novel dyes to organic material which possesses OH, NH or NH groups is done forn aqueous solution, and may be efiected by several procedures such as padding, exhaust, printing or (in the case of azo dyes) development on the fiber. All these procedures involve at one stage or another treatment of the fabric also with an aqueous alkali solution and heating. For instance, in padding, two separate baths may be employed, whereby the fabric is first padded in a dyebath then dried and padded in an alkaline bath; or the dye and alkali may be added to the same bath, whereby the fabric receives but a single padding treatment. The heating may involve steaming after the alkaline treatment, with or without an intermediate drying procedure; dry heating (as on a heated drum) after the alkaline treatment, with or without intermediate drying; application of the alkaline bath itself (in the presence of dye or following the dye padding) at elevated temperature (50 to C.), or padding in alkali,

squeezing and then heating the wet fabric. In printing procedures, the alkali is generally incorporated in the.

printing paste, and the printed fabric is dried and heated.

Where the dye is developed on the fiber, the alkaline and heating treatments areapplied to the fiber after impregnation with the component which carries the dihalobenzodiazine-carbonyl radical, but before application of the further treatments necessary to develop an azo dye on the fiber.

The alkaline agents usable for the above purposes are of the same general class as normally used in dyeing with fiber-reactive dyes. Sodium carbonate and sodium hydroxide are the agents most commonly used, and the degree of alkalinity required is typified by a 2% aqueous solution thereof. V

In forming the dyebath for padding or exhaustion, urea or other agents Which assist in dissolving the color may be added. tion of the dye may be prepared first, which is then diluted In' some cases, a concentrated aqueous soln-' to a bath of the desired strength, or, in the case of printing, is incorporated in the printing paste.

In all theabove procedures, the novel dyes of the invention are found to give both rapid and high fixation, and the dyeings obtainedare characterized by good fastness to light and to washing. a

In the dyeing procedures, a reaction between dye and fiber is believed to take place as illustrated by the following typical equation.

In this equation, Cell represents a cellulose radical, G i

represents a 5- or 6-benzodiazine radical of the group consisting of quinoxaline and phthalazine (which bears the Cl-atoms in the heterocyclic ring), while Y representsCl, OH (resulting from hydrolysis) or another O-Cell'radical.

The above modes of application and theory of reaction apply also to other fibers which have OH, NH or NI-I radicals, but obviously high alkalinity or prolonged con-.

tact with alkali are to be avoided in the case of wool or other fibers which are sensitive to alkali.

On the other hand, the novel dyes' of this invention are applicable to wool and nylon also by the ordinary dyeing procedures recognized for these fibers, that is from a hot, dilute acidic bath as is customary in the art' of dyeing with acid dyes. a v

Without limiting this invention, the following examples are given to illustrate our preferred mode of operation.

Parts mentioned are by weight.

PART I.'PREPARATION OF THE DIHALO- BENZODIAZINE CARBONYL HALIDES Example 1 .--2,3-dichl0r0-6-huinoxa line-carbonyl chloride 15 parts of 3,4-diaminobenzoic acid are added i030 parts of 2B alcohol (95% ethanol) containing 9 parts addition of ice. The solid is filtered oii, dried below/40 C., and recrystallized from parts of cyclohexane, to

'yield 2,3-dichloro-6-quinoxaline-carbonyl chloride, of

M.P. 112-113 C.

4 If the same procedure is carried out, except using 2,3- diaminobenzoic acid in lieu of the 3,4-diaminobenzoic acid above mentioned, 2,3-dichloio-S-quinoxaline-carbonyl chloride is obtained.

Example 2.1,4-dichloro-6-phthizlazine-carb0nyl chloride To 2.4.6 parts of trimellitic'anh-ydride slurried in 100 parts of glacial acetic acid, is added at reflux temperature and over a one half hour period a solution of 5 parts of hydrazine hydrate in 30 parts of glacial acetic acid. The resulting slurry is refluxed 4 to 8 hours, cooled and filtered.

The filter cake, 1,4-dihydroxy-6-phthalazine-carboxylic acid, is washed with 10 parts of glacial acetic acid, dried, and added; to a mixture of parts of phosphorus pentachloride and 15 parts of phosphorus oxychloride. The slurry is heated to reflux (110 to 120 C.), held for 3 to 4 hours at thistempera ture, cooled, and diluted with parts of petroleum ether (B.P. 30 to 60 C.). The precipitated colorless solid is filtered, rinsed with 5 parts of ice-cold acetone, and dried to yield 1,4-dichloro-6-phthalazine-carbonyl chloride, of M.P. l30-l32 C.

In like manner, if hemimellitic anhydride is used in lieu of the trimelliticanhydride in the above example, 1,4- dichloro-5-phthalazine-carbonyl chloride is obtained.

Example 3 Byf-ollowing the procedure of Example 1 or 2, except using a mixture of PBr and POBr in lieu of the mixture of PO1 and P001 there indicated,,the compounds 2,3- dibromo-6-quinoxaline carbonyl bromide and 1,4-di- 'br-omo-6-phthalazine carbonyl bromide, respectively, are

obtained. 7 V

PART .Il.-PREPARATION OF FIBER-REACTIVE 'DYES Throughout these examples and tables which accompany them, an arrow inserted between the names of two compoundsstands for the words: diazotized and coupled to.

Example 1. Az0 dye 8.9 parts of the azo dye, 2-amino-4,8-naphthalenedisulfonic acid fi aminoacetanilide, are dissolved in 250 parts of Water. After adjusting the pH (by the aid of sodium bicarbonate) to about 8 and the temperature to a 35 C., 5.0 parts of 2,3-dichloro-6-quinoxaline-carbonyl chloride (prepared as in Example 1, above). are added. The mixture is stirred overnight at the above temperature and pH, then salted with 12 parts of sodium chloride, whereupon the precipitate formed is filtered off, washed with an aqueous (5%) NaCl solution and dried in a vacuum at a temperature below 60 C.

The light-yellow product obtained corresponds to the formula NHOOCHa When this dye is applied to cotton fabric by the procedure of Example A to C below, a bright yellow dyeing is obtained that exhibits excellent fastness to light, washing 7 and acid perspiration, andhas good bleach fastnes s.

A dye of similar shade and dyeing qualities is obtained 7 if thequinoxaline compound above named is replaced by an equal Weight of 1,4-dichloro-6 phthalazine-carbonyl 70' chloride, prepared as in Example 2, above.

I Dyes of similar high fastness qualities and of shades as indicated below are obtained by condensing the one or the other ofthe abovenamed diazine carbonyl chloride compounds, according to the procedure of theabove example, with any one of the following aminoazo dyes:

TABLE I which exhibits excellent fastness to light, washing, bleach,

and acid perspiration. Shade on Item No Aminoazo dye cotton The initial azo dye used in tl 11s procedure is itself a novel compound and comes within the scope of the r claims of copendin application of R E Starn Jr and 1 8-am1no-1,3,6-na hthalene-trrsulfomc Yellow.

8 acid ma lagiliile. H D W. H. Gumprecht, Serial No. 800,931, filed March 23,

2 -amu1o- -nap1 1216116- risu 01110 0.

acid 3, ammoacemnmde I 1959, now US. Patent No. 3,117,958. It may be prepared 3 Orthatnilic1azcid1fd G-amino-l- Orange. by procedure analogous to that set forth in EX-ample .1 of no t0--su onicaci. L

4 2 amlgno p bemenedisuuomc may send applicat on, and Wh1ch 1S,'1I1 brief outline, as follows. diazgtgzgd and C(illp1e(;l1l2:13 1f P 4-arn1n0-4 -n1trost1lbene-2,2 -d1sulfon1c acid is draw- 5 2-amino-4-methoxybenzenesulfonic acid Orange.

6 ammo 1 naphthowsuuoni c hypochlorite to form the naphtho trlazole compound. acid. After recovery of the latter by saltlng out and filtration, 1t

6 55235?g gegg gf ggggitg is redissolved in water at pH 4 (using acetic acid) and 7 ortha r i igc a cid -a S ruino-l- Red. reduced with iron filings at 100 C. After filtering, the

nap 0- ,6- isu onic aci 8 Mmm 4 methy1benzgngsulfomc Do. solution of the result ng 4 amino compound is diazotized, alcid]f d 8-amino-1-naphth0l-3,6- coupled in acid medium to N-methyl-anlline, and salted.

9 3.3530951,thylbenzsndsummc D0 y vslmllar Shade d g y ng qualities 1 id 8-am1n0-1-naphth01-3,6- obtained if the procedure of this example 18 repeated ex- 10 s-otiiiiio g r itntnaieno-disnironio Do, Clipt using as f azine reagent 2,3-dichloro-6-quinoxalinetd 8-amino-1-naphthol-3,6- carbonyl chloride.

11 fig figfig fl Dyes of similar high fastness qualities and of shades as a efixg i f fi dlazotlzed indicated below are also obtained by the same procedures an R n% vio1et as in this example, except for replacing the aminoazo dye m-Toluldme there named by the stoichiometrically equivalent quantity of any of the aminoazo dyes listed in the following (The amino-monoazo compound named in items 6 and Table H:

11 above is obtained by reduction of the corresponding 4- nitrophenylazo compound, as described more fully in co- TABLE II pending application of W. H. Gumprecht and D. J. Reif, Item Ammoazo dye shade on Serial N0. 830,733, filed July 31, 1959.) cotton The procedural details of the above example may likewise be varied considerably. For instance the vol- 1 3-flmi1w-1t5-nallhthalene-diwlfonicacid Yellow N-methyl-rn-t01uidine. ume Of Water Us d 15 n crltlcal- In hell of Sodlum 2 B-amino-l,5-naphthalcnedisulflmic acid Orange carbonate, sodium hydroxide, trisodium phosphate and Y1-2,fi-dimothory-annine.

3 4-amino-2,7-naphthalcne-dlsul1onic acid, the like may be used to control the pH, and the latter dimmed and coupled 1 (a) N-methylaniline Yellow may be dept at a value between 6 and 10. The condensa (b) N (2 hydmxyethyl)anflme Do tion temperature may vary from 5 to 85 C., and the (c) N-(2-cyan0ethyl)anil ine Do. reaction time from 1 to hours. The quantlty of elec- 40 (d) gg g g lgg (Na trolyte used to salt out the product is likewise not criti- 4 1-(4-amin0phcnylazo)-2 naphthyl-aminec 31 2,3,61-t(riistulfonie acid, diazotized and coupe 0:

Example Il.Azo dye (a) N-n-butylaniline Violet (b) N-methyl-m-toluidinc Do. 30 parts of the amino-azo dye :N S0311 S0311 are dissolved at 40 C. in 600 parts of water. The red Example III.-Az0 dye. Alternate process. Condensing solution is cooled to 16 C., the pH is adjusted with 55 the carbonyl halide with the coupling component sodium bicarbonate to about 7.5 to 8.0, and 10 parts of (a) Preparation of Solution of coupling component 114"dichloro'6'phthalazine'carbOnyl chlonde dissolved i 31.9 parts of 8-amino-l-naphthol-3,6-disulfonic acid are 9 P r of acetone are added- The resulfimg Slurry dissolved in 2000 parts of water, followed by addition of mamtamed at to 200 for 3 hourfi whlle the PH 15 15 parts of sodium formate. 26.2 parts of 2,3-dichloro maintained between 7 and 8 by the addition of an aqueous G0 6 quinoxa1ine carbonyl chloride are then added at solution of sodium bicarbonate. The resulting yellow dye to 5 C. and PH 5 to 5 (held constant by h i. is Salted from 501mm? by the afidition of 200 Parts of tion of 2 N sodium carbonate) over a period of 4 hours. Saturated aqueous sodium chlonde: filtered Washed The condensation mass is stirred overnight at 20 to 25 with 4 parts of sodium chloride in 80 parts of Water, and c. and pH 4.5 to 5.0, then warmed to 50 c., and filtered. dfid below in Vacuum desiccator- The P 65 The filtrate is salted with 300 parts of sodium chloride,

is a sodium Salt which in i s fr e a id rm C 6 P cooled to 18 C. and filtered. The resulting green-brown to the formula filter cake is slurried at room temperature in 2000 parts CH3 t 3 :N SOQH SIOSH H03s- S0311 01-0 0-01 dissolves in water to give a yellow solution. of water, the pH is adjusted to 7.0 by addition of sodium When applied to cotton fabric by any of the procedures bicarbonate, and 60 parts of sodium bicarbonate are A to C hereinbelow, a bright yellow dyeing is obtained, added.

.(b) Preparation of the diazo solution" and coupling.- 25.3 parts of 2-amino-p-benzenedisulfonic acid in 600 parts of water are diazotized with sodium nitrite in the presence of HCl in the usual manner. The pH of the diazo solution is adjusted to 4.9 by addition of 2 N sodium carbonate, and the mass is then stirredinto the above solution of coupling component, over a period ofone hour. The resulting red solution is salted by adding 450 parts of sodium chloride. The red precipitate is filtered ofi,:washed with 50 parts of a 15% sodium chloride solution, and dried.

The color obtained isa sodium salt of the compound defined by the formula:

. S0311 on 1I1'H.C0

I N Hogs HOaS- SOaH and when applied to cotton by the procedures of Examples A and C below, gives bright red dyeings which possess excellent fastness to light and washing, and good acid perspiration fastness.

(c) If 17.3 parts of orthanilic acid are used in place of the 25.3 parts of 2-amino-p-benzenedisulfonic acid in part (b) above, a sodium salt of the compound defined by the formula Gama Hogson I IH-oo SOaH is obtained. This compound is of red-orange shade,.and'

when applied to cotton by the procedures of Examples A to C below, ,it gives bright red dyeings of excellent fastness to light, washing and acid perspiration.

A dye of similar properties is obtained when S-amino-lnaphtho1-3,6-disu1 fonic acid is condensed as above with l,4-dichloro-6-phthalazine carbonyl chloride, and then coupled to diazotized orthanilicacid.

of the shades indicated below may be obtained in a similar manner by condensing 2,3-dichloro-6-quinoxalinecarbonyl chloride with the coupling components listed below, and then coupling to the diazotized amines tabulated.

Example I V.Az dye Developed on the fiber A 4% solution of the green-brown coupling component,

prepared from the filter cake obtained in the first step of Example III, is padded on cotton fabric at 50% pick-up. The fabric is dried, padded at 50% pick-up with a 1.5% aqueous solution of sodium carbonate, steamedfor 30 seconds, and rinsed. The treated fiber is then immersed in a cold diazo solution of Z-arnino-p-benzene-disulfonic acid (prepared in known manner from the amine, .HCl

. 45. Other fiber-reactive dyes of high fastness qualities and .and NaNO containing sufiicient alkali to efiect coupling with the coupler applied to the fiber. The latter is then scoured, rinsed and dried. A red dyeing is obtained, identical in shade and fastness with that obtained by the 'dye ofjExample 111(k); If the diazo compound in the above coupling bath is replaced by the diazo compound of any of the following amines, dyeings of the shades indicated below and of good fastness qualities are obtained.

' TABLE IV Diazo component Shade on fiber 4-arnino-2-methylbenzene-sulfonic acid- Blue-red.

' 4-arnino-3-methylbenzene-sulionic acid. Do.

2-am'ino-3,(i-naphthalene-disulionic acid .s Maroon. 2,5-dimethoxyaniline Blue-purple. 2-methoxy-5-methylaniline Purple. et-methoxy-Z-nitroaniline. Brown. Z-methoxy-i-nitroaniline Purple. c-Anisidine Maroon. p-Anisidine Do. 3-amino-4-methoxybenzencsultonic acid Do. p-Nitroaniline D0. Orthanilic acid Red. 2A dichlor iline Do.

Example V.'-Azo dyes. Alternate process. Condensing the carbonyl halide with the component to be diazotized Preparation of the. diazo s0lution.3.6 parts of 2,4- diamino-benzenesulfonic acid are dissolved in 100 parts of water.v 5 parts of 2,3-dichloro-6-quinoxaline-carbonyl chloride are then added at 20 to 25 C. and pH 7 to 8 over a period of 4 hours. T he resulting solution is cooled to 5 C., and the pH is adjusted to 5.2 by addition of 2 N hydrochloric acid. The'condensation product thus obtained is diazotizedin the usual manner with hydrochloric acid and sodium nitrite, at 5 to 10 C. After stirring for 1 hour at 5 to 10 C., the excess nitrite is destroyed. The pH .is then adjusted to5.1 with an aqueous solution of sodium bicarbonate.

Preparation of coupling component and coupling step.-5.4 parts of 6-acetamido-l-naphthohB-sulfonic acid are dissolved in 100 parts of water. The pH of the solution is adjusted to 7.2 with a solution of sodium bicarbonate, followed by the addition of 4 parts of sodium bicarbonate. The .above mentioned diaZo solution is stirred into the solution of coupling component, at room temperature, to give a bright orange colored solution. Upon addition of sodium chloride (sufficient to form a 15% salt solution) an orange precipitate is obtained, which is filtered off, washed with 20 parts of 10% sodium chloride solution, and dried. The product corresponds to the formula on some I CHsCO-NH V -SOaNa NHCO C1 a N When applied to cotton by any of the procedures A to C below, it produces bright orange dyeings which exhibit excellent f-astness to light and to washing.

If the above procedure is repeated except that the 2,4- diaminobenzene-sulfonic acid is replaced by 3.6 par-ts of 2,5-diaminobenZene-sulfonic acid, the quinoxaline-carbonyl chloride is replaced by 5 parts of 1,4-dichloro-6- phthalazine-carbonyl chloride and the condensation of these two compounds is performed in 150 parts of Water,

' a dye of the following-formula is obtained:

When applied to cellulosic fiber by the above alluded to fiber-reactive procedures, this dye gives bright scarlet dyeings having excellent fastness to light, washing and acid perspiration tests.

Ina similar manner, dyes of the shades indicated below and of excellent fastness properties may be produced by using, in the procedure set forth hereinabove, the following diamines and coupling components The dyes in this example and table may also be produced directly on the fiber, for instance by first fixing onto the fiber (by any of procedures A to C below) the condensation product of any of the above diamines with a dihalogen benzodiazine halide, then diazotizing on the fiber and developing with any of the above tabulated couplers.

Example VI.Metallizea' azo dye. Copper. By condensing with the intermediate 4.6 parts of J acid (6-amino-1-naphthol-3-sulfonic acid) are stirred overnight with parts of 1,4-dichloro-6 phthalazine-carbonyl chloride in 200 parts of water at pH 8, at room temperature. The condensation product is salted out, filtered 01f, washed 'with 5% NaCl solution and dried. The product thus prepared is dissolved in 200 parts of water, the solution is adjusted to pH 7.5 (with sodium bicarbonate) and then cooled to C. This comprises the coupling component for the azo dye.

3.6 parts of 2-amino-1-phenol-4-sulfonic acid in 100 parts of water are diazotized at 5 C. in the usual manner with HCl and sodium nitrite. After a 1 hour period, the excess nitrite is destroyed. The pH of the solution is adjusted to 7.5 with sodium bicarbonate and the temperature is raised to about 10 to C. This diazo solution is then added to the above basic solution of coupler, maintaining the pH at about 7.5 with solid sodium carbonate, and the temperature at 10 to 20 C. The coupling mass is allowed to warm to room temperature and is stirred 'for 48 hours at about pH 7.5.

Metallization.To the resulting orange solution of the monoazo dye at C. are added 3.05 parts of copper sulfate (CuSO in parts of water at pH 7. The rubine solution is stirred for 2 hours at C. and salted to 8% (8 parts NaCl per 10 parts of solution) to give a rubine solid which is filtered oif, rinsed and dried.

The dye thus obtained has the structure 0 When applied to cotton fiber by fiber reactive procedure as discussed above, it gives a rubine shade of excelllent wash, light and bleach fastness.

v 10 Example VII.Metallized azo dye. Copper.

densing with the metallized dye By con- Diazotization and c0upling.3.6 parts of Z-amino-lphenol-4-sulfonic acid in 100 parts of water are diazotized as in Example VI and coupled, at pH 9 to 10, to 4.6 parts of 1 acid in 200 parts of water. The pH is then adjusted to 6.5, and 2 parts of sodium acetate are added.

Metallization.-To the buffered solution thus obtained are added 3.05 parts of copper sulfate; the temperature is raised to C. and is held for 1 hour. The resulting rubine solution is salted to 15% using NaCl, and the rubine solid is filtered ofi and washed with 50 parts of saturated salt solution.

Condensation.-The rubine solid from above is dissolved in 300 parts of water at 15 to 20 C. The pH is adjusted with sodium bicarbonate to pH 7 to 8, and is maintained at this value While the mass is condensed with 5.0 parts of 1,4-dichloro-6-phthalazine-carbonyl chloride. After stirring overnight at room temperature, the condensation is complete. The solution is salted to 8% NaCl concentration, and the rubine dye is filtered off, washed and dried as above. Its structure is the same as in part A of this example.

Example VIIl.Metallized azo dye.

Diazotization and coupling.5.46 parts of 1-amino-6- nitro-2-naphthol-4-sulfonic acid are diazotized in 200 parts of water at 5 to 10 C. with HCl and NaNO The temperature is allowed to warm slowly to 15 to 20 C., the excess nitrite is removed by aid of sulfamic acid, and the pH is adjusted to 7 with solid sodium formate. This is the diazo solution.

4.6 parts of J acid are dissolved in parts of water, and the pH is adjusted to 9.3 by the addition 10 N Na CO solution. This is the coupler solution.

The above diazo solution is added to the solution of coupler over a 1 hour period while maintaining the pH at 9 to 10. The coupling reaction is completed by continued stirring overnight at this pH.

Metallization.The pH of the above solution of amino azo dye is now adjusted to 7.0 with 10 HCl. 2.0 parts of sodium acetate and 20 parts of a solution of sodium chromosalicylate containing 2.5% chromium are added. The solution is refluxed for 4 hours and results in a greenish gray solution.

Condensation-The greenish gray solution is adjusted to pH 7 to 8 and maintained there with trisodium phosphate solution, While being reacted with 5 parts of 2,3- dichloro-6-quinoxaline-carbonyl chloride, at 40 to 50 C., overnight. The mass is now salted to 10% NaCl concentration; the gray solid is filtered off, washed with 25 parts of 10% NaCl solution and dried.

'lihe gray solid, thus obtained corresponds to the formu a Chromium When dyed on cotton by the various application methods discussed above, it yields a greenish gray shade which has good light, wash and bleach fastness.

Example IX .--Acid anthraquinone dye 28 parts of 1-amino-4-(3-amino-4-sulfoanilino)-2- anthraquinone-sulfonic acid (prepared by the condensation of 1-amino-4-bromo-2-anthraquinone-sulfonic acid with 2,4-diaminobenzene-sulfonic acid) are dissolved in 3000 parts of water, and the pH of the solution is adjusted to 7.2 by the addition of a concentrated solution of trisodium phosphate. 15 parts of 2,3-dichloro-6-quin- 'oxaline-carbonyl chloride.

in Example ]X and constitutes a sodlum salt of-a comoxalinecarbonylchloride are added to the blue solution, r

over a 3-hour period, at 35 to 45 C., while maintaining the pH at 7.5 to 8.5; by the addition of trisodium phosphate. The resultingthick slurry is allowed to cool to room temperature while stirring overnight. After salting with 300 parts of sodium chloride, the'blue. precipitate is filtered ofl, washed with 50 parts of a 4%, sodium chloride solution, and dried .in a'vacuum desiccator below 60 C. The product is a sodium salt of the compound defined by the formula I .NH; I!

Nit-0o V When: applied to cotton fiber by the procedures of Examples A to C below, it produces bright blue dyeings of excellent fastness to light, washing and acid perspira- A dye of substantially the same shade and qualities is 1 obtained if the quinoxaline compound in the above example is replaced by 15 parts of 1,4-dichloro-6-phthalazine-carbonyl chloride. V

Example X 29.8 parts of 1-amino4-(4-methylamino-3-sulfoanilino)2-anthraquinonesulfonic acid (prepared by thecondensation of 1-amino-4-bromo-2-anthraquinonesulfonic acid with 4-methylan1ino-3-sulfoaniline) are condensed I a 1.2 o Example XI.Phthalocyartine dye Preparation of water-soluble'coppe r phthalocyanine intermediqte.'-5.76 parts .of copper;phthalocyanine are slowly added below 25C. to 41 parts of-chlorosulfonic acid. The solution is slowly heated to 130 C., and held for 3 hours, cooled, and drowned below- 5 C. in an agitated mixture; consisting of 100 parts of cold water, 300 parts of ice and parts of' sodium chloride. The

solid is then filtered 01f and washed with 500 parts of.

5% sodium chloride solution. This represents copper phthalocyanine polys'ulfonylchlor'ide press cake.

This press cake is now slowly added at pH 6 to 6.5 (maintained by'the addition ofsodium carbonate) to a solution of 4.34 parts of p-phenylenediaminein parts of water. The turquoise solution is warmed and agitated at 60 C., until the pH remainsconstant. The reaction mass is then cooled and salted to 20% saltconcentration by addition of sodium chloride. The solid is filtered off and washed with 100 parts of 15% salt solution. It constitutes a compound of the formula V ,CuPc

wherein x and y are average numbers of which x is not less than, 1, is not less than 2, and the-sum of the two is between 3 and 4, while CuPc represents a molecule of copper phthalocyanine less (x+y) H-atoms.

Condensation.The filter cake obtained, above is dissolved in 200 parts of water, the pH is adjusted to about 7.5 to 8. by'addition of sodium bicarbonate, the temperature'is raised to about 40 to 50 C. and 5.2 parts of as in Example IX with 15 parts of 2,3-dichloro-6-quin- The product is recovered as pound defined by the formula SOaH When applied to cotton by the procedures of Part III hereinbelow, this compound producesbright blue dyeing of excellent fastness to light, washing and acid perspiration.

Dyes of similar fastness qualities and of shades as indicated below are obtained if the procedureofExample IX is repeated with any of the followingacid anthraquinone dyes as initial materials:

2,3-dichloro-6-quinoXaline-carbonyl chloride are added. The condensation is allowed to proceed for 12 to 15' hours under agitation at said temperature. The solution is salted to. 15 sodium chloride. The resulting turquoise dye is filtered ofi, washed with parts of 20% salt solution and dried.

The dried cake represents a compound of the formula hereinabove, but wherein at least some of the moisten-ONE:

groups-have been replaced by side-chains of the formula I V e N .-so,N11-ONHoo- -o1 When applied to cotton by the methods outlined above,

' it afiords bright turquoise shades that are fast to washing and to light.

Similar results as in the above example may be obtained by startingwith a sulfuric acid-stable metal phthalocyanine, such as nickel or cobalt phthalocyanine, in lieu of copper phthalocyanine. Also, by changing the nature of the diamine selected, the quantity thereof, and the conditions of chlorosulfonation, phthalocyanine compounds of the general formula may be obtained and used .as-i'nitial dye for condensation with dihalogeno-benzodiazine-carbonyl halides. In this formula,x and y are average numbers adding up to between 2 and 4' (each being at least 1); MPc represents a metal phthalocyanine which is stablein the chlorosulfonationreaction (for instance,'nickel or cobalt phthalocyanine), while Ar may represent miscellaneous substituted phenylene diamines, benzidines or diaminostilbenes,

as typified by the following table.

1 3 TABLE v11 2,5-diaminobenzene-sulfonic acid; N-rnethyl-p-phenylenediamine; N-Z-hydroxyethyl-p-phenylenediamine; N-Z-cyanoethyl-p-phenylenediamine; N-2-sulfatoethyl-p-phenylenediamine; S-amino-Z-ethylaminobenzene-sulfonic acid; 4,4-diamino-3,3-biphenyl-disulfonic acid; 5-amino-2-n-propylamino-benzenesulfonic acid; 4,4-diamino-2,2'-biphenyl-disulfonic acid; 4,4'-diamino-2,2'-stilbene-disulfonic acid; m-Phenylenediamine; 2,4-diarninobenzene-sulfonic acid; N-methyl-m-phenylenediamine;

N- (Z-hydroxyethyl) -m-phenylenedi amine; N-isobutyl-m-phenylenediamine; ,4-amino-2-methylamino-benzenesulfonic acid; 4-amino-2-n-butylamino-benzenesulfonic acid; Toluene-2,5-diamine;

Toluene-2,4-diamine.

Similar results are obtained further by using in lieu of the sulfamido arylamino substituted phthalocyanines above formulated, phthalocyanine compounds which bear amino groups on an aliphatic side-chain, for instance the compound (CH NH 'HCIh CuPc (sour); Example X 11 Copper phthalocyanine polysulfonyl chloride press cake, obtained as in Example XI from 5.76 parts of copper phthalocyanine, is slurried at pH 6 and 40 C. in 150 parts of water containing 4.1 parts of the condensation product of 2,4-diamino-benzenesulfonic acid with 2,3-dichloro-6-quinoxaline-carbonyl chloride (prepared as in Example V). After four hours stirring at this tempera ture and pH, the blue solution is salted, and the dye is filtered off and dried. It constitutes a sodium salt of the dye represented in the free acid form by the formula (U.S.P. 2,761,868)

wherein x and y are average numbers of which x is not less than 1, y is not less than 2, and the sum of the two is between 3 and 4. When applied to cotton by the methods of Part III hereinbelow, this dye produces bright turquoise shades, which are fast to washing and to light.

In lieu of 2,4-diamino-benzenesulfonic acid in the above condensation, other arylene diamines may be used, for instance, p-phenylene diamine, m-phenylene diamine, or 2,5-diaminobenzene-sulfonic acid.

PART III.APPLICATION TO FIBER One-pad procedure.-Cotton fabric is padded with a solution of dye, urea and sodium carbonate and/ or sodium bicarbonate. The padding is cured by drying and heating at 390-425 F. for 30 seconds or more, thereafter cooled, rinsed, scoured, rinsed and dried. The urea may be eliminated from the dye bath without changing the quality of the dyeing.

Specific examples illustrating this process are as follows:

Example A 30 parts of the yellow dye of Example I are dissolved in 1000 parts of water containing 10 parts of sodium carbonate- This solution is padded onto cotton broad cloth at 65% pick-up, the fabric is dried in a flue dryer, passed for 45 seconds through a 390 F. oven, washed (hot water rinse, cold water rinse, hot soap scour, hot water rinse and cold Water rinse) and dried. There results a bright yellow shade which is fast to washing and light.

When 200 parts of urea are added to the dye bath, a dyeing of equal shade, strength and fastness results.

Example B One part of the dye of Table VI, item No. 3, is dissolved in 1000 parts of water containing 10 parts of sodium bicarbonate and 50 parts of urea. This solution is padded onto cotton twill at pick-up, the fabric is frame dried, passed for seconds through a 425 F. oven, washed and dried. There results a light blue dyeing which is fast to washing and light.

When the urea is omitted from the dye bath, a dyeing of equal shade, strength and fastness results.

Example C 10 parts of the dye of Example III, paragraph C, are dissolved in 1000 parts of water containing 20 parts of sodium carbonate. This solution is padded onto a 65:35 blend of polyester fiberzcotton, the fabric is dried on a can dryer, passed for 90 seconds through a 400 F. roller-type curing oven, washed and dried. There results a bright red dyeing which is fast to washing and light.

When a disperse dye such as Latyl die is added to the dye bath of this process, one gets simultaneous dyeing of the Dacron and the cotton.

Example D 50 parts of the dye of Example XII are dissolved in 1000 parts of water containing five parts of sodium carbonate and 15 parts of sodium bicarbonate. This solution is padded onto cotton poplin, the fabric is dried with an infra-red predyer, padded for 60 seconds through a 390 F. curing oven, washed and dried. There results a bri ht turquoise dyeing which is fast to washing.

Example EPrinting When disperse dyes and the fiber-reactive dyes disclosed herein are formulated together in printing compositions containing acid acceptor selected from the group of alkali metal carbonates and bicarbonates, and the printing com- 7 position is applied to fabrics of blended polyester and Parts Monochloro 4,8 diaminoanthrarufin, finely dispersed 30 The dye of structure shown in Example X 20 Keltex-sodium salt of alginic acid (Kelco Co.,

Clark, NJ.) 20 Urea m-Nitrobenzenesulfonic acid, sodium salt 10 Sodium bicarbonate 20 Water 800 Total 1000 is printed onto fabric consisting of a 65:35 blend of Dacron polyester fiber and cotton. The fabric is dried, passed for 90 seconds through a 400 F. curing oven, rinsed in cold water then in hot water, washed in a hot solution of nonionic detergent followed by a dilute (0.1%) acetic acid rinse, rinsed in water, and dried. The fiber components of the fiber blend are dyed in blue shades which are fast to washing and to light.

If desired, the Keltex thickener used in the present example may be replaced by other thickeners such as methylcellulose, starch ethers and the like. Also, the sodium bicarbonate may be replaced by sodium carbonate.

It is to be understood that any of the dyes in the above Examples 1 to XII or prepared from the intermediates spirit of the'invention.

For instance, in lieu of the 2,3-dichloro-6-quinoxalinecarbonyl chloride wherever named in the above examples, the stoichiometric equivalent of any of the following dia- Zines may be used: a

2,3,-dichloro-S-quinoxaline-carbonyl chloride; 1,4-dichloro-6-phthalazine-carbonyl chloride; 1,4-dichloro-S-phthalazine-carbonyl chloride; 2,3-dibromo-d-quinoxaline-carbonyl bromide; 1,4-dibromo-6-phthalazine-carbonyl bromide.

The azo dyes named in Examples I'and'II, may be replaced by theoretically equivalent quantity of any azo dye having the requisite water-solubility by virtue of possessing sulfo and/ or carboxy groups and having an acyl- 'atable amino group. Likewise, the diazo components and coupling components named in Examples III and IV may be replaced by theoretically equivalent quantities of any combination of a diazo component and a coupling component which will result in a dye having the requisite water-solubility. Some alternatives have been specifically named in the mentioned examples. Others worthy of special consideration, because they are'readily available or lead to desirable shades, areindicated in vthe following tables of diazo components and coupling components and by the azo dyes which result from coupling these in various combinations from these tables or with the coupling components or diazo components, respectively, named in Examples Ito V Alternative coupling components: m-Anisidine, N-ethyl aniline, N-ethyl-m-toluidine, N-n-propyl-m-toluidine, 3' aminoacetanilide, 5 amiho-Z-naphthalenesulfonic acid, l-naphthol-3,6,8-trisulfonic acid, S-amino-l-naphthl-3-sulfonic acid, 6-ethylamino-1-naphthol-3-sulfonic acid, 6-amino-1-naphthol-3,5-disulfonic acid.

Alternative diaZo-azo components? 4-amino-4'-nitro-2,2-stilbenedisulfonic acid- 1-naphthol3,6,8-tris'ulfonic acid (and reduction of the 4'- nitro group to an amino group); p a

2 amino-p-berlenedisul-fonic acid- 5-amino-2-naphthalenesulfonic' acid;

Sulfanilic acidorthanilic acid;

2-amino-4-nitrobenzene-sulfonic acidcresidine; 3-arnino1,S-naphthalene-disulfonic acid cresidine.

In Example V, any of the diamines there named may be replaced by m-phenylene-diamine or p-phenylenediarnine, while the coupling'components may be replaced by any of the alternatives named hereinabove as well as 6- or S-acetamido-l-naphthol-3-sulfonic acid, S-acetamido-1-naphthol-3,6-disulfonic acid, 8-benzamido-1-naphthol-3,6-disulfonic acid, 7-amino-1 naphthol-3,6-disulfonic acid, 6-amino-1,3-naphthalenedisulfonic acid, 2-naphtho13,G-disulfonic acid or 3-amino-2,7-naphthalenedisulfonic acid.

In Examples VI VII and VIII, the metallizing agents (Cu and Cr) may be interchanged or they may be replaced by reagents which will introduce nickel or cobalt as metal 1 into the azodye. The. latter itself (in each example) may Y 2-amino 4 methyl-l-phenol-S-sulfonic acid 6-amino-1-,

naphthol-3-sulfonic acid;

" Z-amino 4 sulfobenzoic acid 6-amino-1-naphthol-3-sul- I fonic acid;

2 amino-G-nitro-l-phenol-4-sulfonic acid- 6- (4-amino-3- sulfoanilino)-1-naphtho1-3-sulfonic acid;

2 amino-'-nitro-1-phenol-4-sulfonic acid- 3-methyl-1-(psulfophenyl)-5-pyrazolone (and reduction of the nitro group to an amino group); i

Z-amino-S-nitrobenzoic acid- 3-methyl-1-(p-sulfophenyD- "S-pyraZolone (and reduction of the nitro group to an amino group);

l-amino 6 nitro-2-naphthol-4-sulfonic acid- 8-amino-1- naphthol-S-sulfonic acid;

1-amino-6-nitro-2-naphthol4-sulfonic acid, diazotized and coupled to: o

' 2-naphthol-6-sulfonic acid 0 3 -methyl- 1- (m-sulfophenyl) 5 -pyrazolone,

andfollowedin each instance by reduction of the nitro group to an amino group.

In Examples IX and X, the acid anthraquinone dyes 'named there may be replaced by any other dyes of this class, for instance any one of the following:

' 1-amino-4-(p-beta hydroxyethylarnino-anilino)-2,5-

anthraquinone-disulfonic acid; 1-a1nino-4-(p-beta-cyanoethylamino-anilino)-2,3-

anthraquinone-disulfonic acid; 7 1-amino-4-(p-beta-sulfatoethylamino-anilino)-2,3-

anthraquinon'e-disulfonic acid;

. 1-amino-4-(3-carboxy-4-methylaminoanilino) -2,6-

anthraquinone-disulfonic acid;

, 1,4-bis(4aamino-3 -sulfoanilino -anthraquinone;

l-amino-4- (2-carb oxyanilino -3 -anthraquinone-sulfonic acid;

1-amino-4: [p- (4-an1ino-3 -sulr'ophenyl) anilino] 2,5-

anthraquinone-disulfonic acid;

I 1-amino-4-.[4- (4-amino-2sulfophenyl) -3-sulfoanilino]- Z-anthraquinonesulfonic acid; 1-amino-4- [4-(4-amino2-sulfostyryl) -3 -sulfoanilino] Z-anthraquinonesulfonic acid;

4,8-bis(4-amino-3 sulfoanilino)-1,5-dihydroxy-2,6-

The acid-anthraquinone dye of formula NH; II I sO N oH o0o1n T e acid anthrapyrimidine dye of formula N= =0 soar In the sailing out step in each example, the quantity of salt employed may vary widely, and this can be readily determined by observing the volume r rate of precipitation of the dye. In some instances, where the solid dye product separates readily on cooling, the salting step may be omitted altogether.

The salted out dye in any of the examples may be converted into free SO H form by acidification and the latter may then be converted into vater-soluble salts by treatment with customary, water-soluble bases, for instance, NaOi-l, KOH, ammonium hydroxide or water-soluble organic amines.

in selecting the dye chromophore, it may be well to observe that those compounds wherein the R in the group is an alkyl radical of l to 4 C-atoms and wherein the remainder of the dye molecule is free of OH, NH and NH groups, generally lead to fiber reactive dyes which possess high fastness to bleach, in addition to good lightand Wash-tastness. (See Example H and Table ll above.)

in lieu of the acid acceptors for the condensation reaction named in the specific examples (i.e. sodium bicarbonate or trisodium phosphate), other bases may be employed, such as sodium hydroxide, potassium carbonate, sodium acetate, ammonium hydroxide and the like. The pE-l for this reaction is not particularly critical, the operable range being approximately between pH 4 and 10, and the preferred range being about pH 7 to 9.

In the application of the dye to the fiber, the alkalizing treatment may be achieved by any commonly used acid acceptor, for instance sodium or potassium carbonate, an alkali-metal hydroxide, alkali-metal bicarbonates or phosphates, diammonium phosphate, benzyl trimethyl-ammoniurn hydroxide, and the like.

Other permissible variations will be readily obvious to those skilled in the art.

The majority of the reactive dyes of this invention are characterized by high percentage fixation and high rate of fixation on cellulosic fiber; they also possess alkaline stability, which implies little if any loss by decomposition in the pad bath treatment.

By acid anthraquinone coloring matters we mean any water-soluble anthraquinone coloring compound, particularly those which are normally used as acid wool colors. See, for instance, H. A. Lubbs, The Chemistry of Synit; thetic Dyes and Pigments, Chapter on Anthraquinone Acid Dyes, pages 390 to 417, inclusive.

By water-soluble phthalocyanine coloring matters, we mean compounds having the fundamental macrocyclic structure of a metal phthalocyanine, for instance that of Cu[C H (CN) bearing sufficient water-solubilizing groups to solubilize the compound to the extent needed in a dyebath, as above indicated.

By anionic dye chromophore we mean a dye which bears anionic water-solubilizing radicals such as sulfo or carboxy.

The preceding representative examples may be varied within the scope of the present total specification disclosure, as understood and practiced by one skilled in the art, to achieve essentially the same results.

As many apparently widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for dyeing cellulosic fibers with a fiberreactive dye containing a 2,3-dichloro-G-quinoxalinecan bonylamino group, which process consists essentially of the following steps:

(A) the cellulosic fiber is padded with said fiber-reactive dye from a solution consisting essentially of from 0.1 to 60 parts of said dye and from 10 to 20 parts of an acid acceptor selected from the group consisting of sodium carbonate and sodium bicarbonate, per 1000 parts of Water at ambient temperature;

(B) the resulting dye-padded fiber is then dried followed by heating for 45 to seconds at from 390 to 425 F.; and

(C) washing the resulting dyed fiber of step B.

2. A process according to claim 1, which process utilizes from 50 to 200 grams per liter of urea in the pad bath.

3. A process for dyeing and printing fabrics, said fab rics consisting essentially of cellulosic and polyester fibers, in which process a member selected from the group consisting of a printing composition and a padding solution is applied to said fabric, said printing composition and said padding solution containing a member selected from the group consisting of an alkali-metal carbonate and an alkali-metal bicarbonate, a disperse dye and a dye containing a 2,3-dichl0ro-6-quinoxalinecarbonylamino group, followed by drying and heating the treated fabric for 45 to 90 seconds at a temperature of from 390 to 425 F., and washing the resulting dyed fabric.

References Cited by the Examiner UNITED STATES PATENTS 1,886,480 11/32 Haller et al 8-542. X 3,043,650 7/62 Wegmann et a1 81.20 3,082,052 3/63 Booth et a1. 854.2

FOREIGN PATENTS 315,451 7/29 Great Britain. 1,247,660 10/60 France.

NORMAN G. TORCHIN, Primary Examiner. 

3. A PROCESS FOR DYEING AND PRINTING FABRICS, SAID FABRICS CONSISTING ESSENTIALLY OF CELLULOSIC AND POLYESTER FIBERS, IN WHICH PROCESS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A PRINTING COMPOSITION AND A PADDING SOLUTION IS APPLIED TO SAID FABRIC, SAID PRINTING COMPOSITON AND SAID PADDING SOLUTION CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALKALI-METAL CARBONATE AND AN ALKALI-METAL BICARBONATE A DISPERSE DYE AND A DYE CONTAINING A 2,3-DICHLORO-6-QUINOXALINECARBONYLAMINO GROUP, FOLLOWED BY DRYING AND HEATING THE TREATED FABRIC FOR 45 TO 90 SECONDS AT A TEMPERATURE OF FROM 390* TO 425*F., AND WASHING THE RESULTING DYED FABRIC. 